KR20220084087A - Resin composition, photosensitive resin composition, and cured product thereof - Google Patents

Abstract

(식 (NB) 중, R¹, R², R³ 및 R⁴는, 각각 독립적으로, 수소 원자 또는 탄소수 1~30의 유기기이며, a₁은 0, 1 또는 2이다.)
[화학식 2]

(식 (1) 중, R^p는, 2 이상의 (메트)아크릴로일기를 갖는 기이다.)Polymer containing the structural unit represented by Formula (NB), and the structural unit represented by Formula (1); and a compound having two or more (meth)acryloyl groups.
[Formula 1]

(In formula (NB), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a ₁ is 0, 1 or 2.)
[Formula 2]

(In formula (1), R ^p is group which has two or more (meth)acryloyl groups.)

Description

Resin composition, photosensitive resin composition, and cured product thereof

The present invention relates to a resin composition, a photosensitive resin composition, and a cured product thereof. In more detail, it is related with the resin composition, the photosensitive resin composition containing the said resin composition, and hardened|cured material of the said photosensitive resin composition.

A liquid crystal display device and a solid-state image sensor are normally equipped with a color filter and a black matrix. A color filter and a black matrix have a structure in which structures, such as a coloring pattern and a protective film, were formed on the board|substrate. Among these structures, as a method of forming a colored pattern or a protective film, a method of forming by photolithography using a photosensitive resin composition has become mainstream. Regarding the photosensitive resin composition, various studies have been made conventionally, for example, in Patent Document 1, alkali-soluble resin having an acidic group and two or more mutually different polymerizable unsaturated groups in at least a side chain, polymerizable A photosensitive resin composition comprising a compound and a photoinitiator is described. Moreover, in the Example of patent document 1, what synthesize|combined methacrylic acid/allyl methacrylate/glycidyl adduct as alkali-soluble resin, and prepared the photosensitive resin composition using this is described.

Patent Document 1: International Publication No. 2012/147706

Resin provided with the property which a polymerization reaction occurs by light and hardens|cures is used for the photosensitive resin composition for forming a color filter or a black matrix. A color filter and a black matrix are produced by hardening|curing this, after patterning a photosensitive resin composition by exposure and image development. The photosensitive resin composition WHEREIN: Although "sensitization" is considered as a general subject, sensitization of a still higher level is calculated|required with complexity, spread, etc. of a display apparatus and an imaging device. The time required for exposure can become short, so that the sensitivity of the photosensitive resin composition is high, and productivity can be improved. Moreover, it is calculated|required that the photosensitive resin composition be equipped with the outstanding processability in the developing process using an alkaline developing solution.

MEANS TO SOLVE THE PROBLEM The present inventors discover that the photosensitive resin composition excellent in the polymer used for the photosensitive resin composition and the compounding of the said composition is obtained by improving the compounding of the said composition, while having high alkali solubility while a sensitivity is favorable, and therefore, developability, this invention reached

According to the present invention,

Polymer containing the structural unit represented by Formula (NB), and the structural unit represented by Formula (1); and

A resin composition comprising a compound having two or more (meth)acryloyl groups is provided.

[Formula 1]

(In formula (NB), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a ₁ is 0, 1 or 2.)

[Formula 2]

(In formula (1), R ^p is group which has two or more (meth)acryloyl groups.)

In addition, according to the present invention,

Polymer containing the structural unit represented by Formula (NB), and the structural unit represented by Formula (1);

compounds having two or more (meth)acryloyl groups; and

A photosensitive resin composition comprising a photosensitive agent is provided.

[Formula 3]

(In formula (NB), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a ₁ is 0, 1 or 2.)

[Formula 4]

(In formula (1), R ^p is group which has two or more (meth)acryloyl groups.)

Moreover, according to this invention, the hardened|cured material formed from the said photosensitive resin composition is provided.

ADVANTAGE OF THE INVENTION According to this invention, while a sensitivity is favorable, it has high alkali solubility, Therefore, the resin composition as a resin material for use for the photosensitive resin composition excellent in developability is provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure (cross-sectional view) which shows typically an example of the structure of a liquid crystal display device and/or a solid-state image sensor.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described, referring drawings. In addition, in all the drawings, the same code|symbol is attached|subjected to the same component, and description is abbreviate|omitted suitably. In addition, all drawings are for explanatory purposes only. The shape, dimension ratio, etc. of each member in a drawing do not necessarily correspond to an actual article. In the present specification, the expression "a to b" in the description of the numerical range indicates a or more and b or less, unless otherwise specified. For example, "5-90%" means "5% or more and 90% or less".

In the description of a group (atomic group) in the present specification, the expression not describing whether it is substituted or unsubstituted includes both those having no substituent and those having a substituent. For example, "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

The description of "(meth)acryl" in this specification shows the concept containing both acryl and methacryl. The same is true for similar notations such as "(meth)acrylate".

In particular, the "(meth)acryloyl group" in this specification refers to an acryloyl group represented by -C(=O)-CH=CH ₂ , and -C(=O)-C(CH ₃ )=CH ₂ represents a concept including a methacryloyl group represented by

(resin composition)

The resin composition of this embodiment is used as a resin material for producing the photosensitive resin composition. The resin composition of this embodiment contains the polymer P containing the structural unit demonstrated in detail below, and the compound which has two or more (meth)acryloyl groups.

(Polymer P)

The polymer P used for the resin composition of this embodiment contains the structural unit represented by Formula (NB), and the structural unit represented by Formula (1). In addition, these structural units typically constitute the main chain of the polymer P.

[Formula 5]

In formula (NB), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a ₁ is 0, 1 or 2.

[Formula 6]

In Formula (1), R ^p is group which has two or more (meth)acryloyl groups.

The polymer P used for the resin composition of this embodiment contains the structural unit represented by Formula (1). Thereby, the photosensitive resin composition containing the said polymer P has the outstanding sensitivity when it uses the photolithographic method. It is thought that this is because hardening reaction (polymerization reaction) is accelerated|stimulated by 2 or more (meth)acryloyl groups contained in the structural unit represented by Formula (1). Moreover, the polymer P contains the structural unit represented by Formula (NB). This structural unit (NB) is chemically robust. Therefore, when the polymer P containing this as a structural unit is subjected to heat treatment, the weight loss is small and stable. Therefore, the photosensitive resin composition containing polymer P can be used suitably in order to manufacture the film and filter for use for the liquid crystal display device or solid-state image sensor which heat resistance is calculated|required.

In one embodiment, the polymer P contains the structural unit represented by Formula (2) in addition to the said structural unit.

[Formula 7]

In Formula (2), R ^s is group which has one (meth)acryloyl group.

By including the structural unit represented by Formula (2) in addition to the structural unit represented by Formula (1), the polymer P has higher sensitivity and high alkali solubility, and therefore can be suitably used for processing by photolithography. have.

In one embodiment, the polymer P may contain the structural unit represented by Formula (3) in addition to the said structural unit. By including the structural unit represented by Formula (3), the polymer P has higher alkali solubility. As a result, the photosensitive resin composition containing the polymer P has excellent developability when subjected to a photolithography process using an aqueous alkali solution as a developer.

[Formula 8]

In one embodiment, the polymer P may also contain the structural unit represented by Formula (MA) in addition to the said structural unit. The structural unit represented by Formula (MA) is ring-opened with an alkali developing solution, and generate|occur|produces two carboxyl groups. Therefore, the polymer P containing the said structural unit is equipped with the outstanding developability. When the polymer P contains the structural unit represented by the formula (MA), the structural unit represented by the formula (MA) in the total structural units of the polymer P is preferably 1 to 10 mol%, more preferably, 2-7 mol%.

[Formula 9]

In one embodiment, the polymer P may contain a thioether group (-S-) in addition to the said structure. The thioether group is a group derived from a thiol group-containing compound used as a chain transfer agent in the synthesis of polymer P.

In the structural unit represented by the formula (NB) constituting the polymer P, the organic group having 1 to 30 carbon atoms that can constitute R ¹ to R ⁴ is a substituted or unsubstituted, linear or branched chain having 1 to 30 carbon atoms. of an alkyl group, more specifically, an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkaryl group, a cycloalkyl group, an alkoxy group, a heterocyclic group, a carboxyl group, and the like. .

Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group , an octyl group, a nonyl group, a decyl group, and the like.

As an alkenyl group, an allyl group, a pentenyl group, a vinyl group, etc. are mentioned, for example.

As an alkynyl group, ethaneyl group etc. are mentioned, for example.

As an alkylidene group, a methylidene group, an ethylidene group, etc. are mentioned, for example.

Examples of the aryl group include a tolyl group, a xylyl group, a phenyl group, a naphthyl group, and an anthracenyl group.

As an aralkyl group, a benzyl group, a phenethyl group, etc. are mentioned, for example.

As an alkaryl group, a tolyl group, a xylyl group, etc. are mentioned, for example.

Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.

Examples of the alkoxy group include a methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, isobutoxy group, tert-butoxy group, n-pentyloxy group, A neopentyloxy group, n-hexyloxy group, etc. are mentioned.

As a heterocyclic group, an epoxy group, oxetanyl group, etc. are mentioned, for example.

As R ¹ , R ² , R ³ and R ⁴ in the structural unit represented by the formula (NB), hydrogen or an alkyl group is preferable, and hydrogen is more preferable.

In addition, the hydrogen atom in the C1-C30 organic group of R< ¹ >, R< ² >, R< ³ >, and R< ⁴ > may be substituted by arbitrary atomic groups. For example, it may be substituted with a fluorine atom, a hydroxyl group, a carboxyl group, etc. More specifically, as the organic group having 1 to 30 carbon atoms for R ¹ , R ² , R ³ , and R ⁴ , an alkyl fluoride group or the like may be selected.

Structural unit represented by Formula (NB) WHEREIN: A1 becomes like this. Preferably it is 0 or ₁ , More preferably, it is 0.

The proportion of the structural unit represented by the formula (NB) in all the structural units of the polymer P is preferably 10 to 90 mol%, more preferably 30 to 70 mol%, still more preferably 40 to 60 mol%.

In this embodiment, the polymer P has the structural unit represented by Formula (1), in other words, the structural unit containing _two or more (meth)acryloyl groups (-C(=O)-CH=CH2) . Thereby, the sensitivity in the exposure process of polymer P can be improved.

Structural unit represented by Formula (1) which comprises polymer P WHEREIN: R ^p is a group containing two or more (meth)acryloyl groups, Preferably 2-6 pieces of (meth)acryloyl groups are included. It is group which says, More preferably, it is group containing 3-5 (meth)acryloyl groups. By optimizing the number of (meth)acryloyl groups contained in R ^p , the sensitivity in the exposure treatment of the polymer P containing this can be further increased. Moreover, it becomes easy to make the sensitivity of polymer P and alkali solubility compatible more highly. In addition, the heat resistance of the polymer P can be improved.

It is preferable that R ^p is group represented by Formula (1b) or group represented by Formula (1c). With such a group, it exists in the tendency for said various effects to be easy to be acquired.

It is preferable that R ^p in Formula (1) is group represented by group represented by Formula (1b), group represented by Formula (1c), or Formula (1d). With such a group, it exists in the tendency for said various effects to be easy to be acquired.

[Formula 10]

In formula (1b),

k is 2 or 3,

R is a hydrogen atom or a methyl group, and a plurality of Rs may be the same or different,

X ¹ is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -ZX- (Z is -O- or -OCO-, X is an alkylene group having 1 to 6 carbon atoms), and a plurality of X ¹ may be the same or different,

X ¹ 'is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -X'-Z'- (X' is an alkylene group having 1 to 6 carbon atoms, and Z' is -O- or -COO-) is,

X ² is a k+1 valent organic group having 1 to 12 carbon atoms.

R is preferably a hydrogen atom from the viewpoint of further improvement in sensitivity (easiness of polymerization) and the like.

Although the number of k may be 2 or 3 may be sufficient, From the point of the further improvement of the availability of a raw material and a sensitivity, Preferably it is 3.

When X ¹ is an alkylene group having 1 to 6 carbon atoms, the alkylene group may be linear or branched.

When X ¹ is an alkylene group having 1 to 6 carbon atoms, X ¹ is preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 3 carbon atoms, further preferably -CH ₂ -(methylene group).

When X ¹ is a group represented by -ZX- (Z is -O- or -OCO-, X is an alkylene group having 1 to 6 carbon atoms), the alkylene group having 1 to 6 carbon atoms in X may be linear It may be branched.

The C1-C6 alkylene group of X becomes like this. Preferably it is a linear alkylene group, More preferably, it is a C1-C3 linear alkylene group, _More preferably, it is -CH2 _- CH2-(ethylene group) or —CH ₂ —CH(CH ₃ )—.

When X ¹ ′ is an alkylene group having 1 to 6 carbon atoms, the specific aspect thereof is the same as that of X ¹ .

When X ¹ ' is a group represented by -X'-Z'-, specific aspects of X' are the same as those of X above.

Examples of the k+1 valent organic group of X ² having 1 to 12 carbon atoms include any group obtained by removing k+1 hydrogen atoms from any organic compound. The "arbitrary organic compound" herein is, for example, an organic compound having a molecular weight of 300 or less, preferably 200 or less, and more preferably 100 or less.

X ² is, for example, a group obtained by removing k+1 hydrogen atoms from a linear or branched hydrocarbon having 1 to 12 carbon atoms (preferably 1 to 6 carbon atoms). More preferably, it is the group which removed k+1 hydrogen atoms from a C1-C3 linear hydrocarbon. In addition, the hydrocarbon here may also contain the oxygen atom (For example, an ether bond, a hydroxyl group, etc.). Moreover, it is preferable that hydrocarbon is saturated hydrocarbon.

In another aspect, X ² may also contribute including a cyclic structure. As group containing a cyclic structure, the group containing an alicyclic structure, the group containing a heterocyclic structure (for example, isocyanuric acid structure), etc. are mentioned.

[Formula 11]

In formula (1c),

k, R, X ¹ and X ² each have the same meaning as R, k, X ¹ and X ² in formula (1b), and a plurality of R may be the same as or different from each other, and a plurality of X ¹ may be the same as or different from each other,

X ³ is a divalent organic group having 1 to 6 carbon atoms,

X ⁴ and X ⁵ are each independently a single bond or a divalent organic group having 1 to 6 carbon atoms,

X ⁶ is a divalent organic group having 1 to 6 carbon atoms.

Specific aspects and preferred aspects of R, k, X ¹ and X ² are the same as those described in the general formula (1b).

Examples of the divalent organic group having 1 to 6 carbon atoms for X ³ and X ⁶ include a group obtained by removing two hydrogen atoms from a linear or branched hydrocarbon having 1 to 6 carbon atoms. In addition, the hydrocarbon here may also contain the oxygen atom (For example, an ether bond, a hydroxyl group, etc.). Moreover, it is preferable that hydrocarbon is saturated hydrocarbon.

A linear or branched alkylene group is mentioned as a C1 ^- C6 divalent organic group of X4 and ^X5 . The straight-chain or branched alkylene group preferably has 1 to 3 carbon atoms.

[Formula 12]

In formula (1d), n is an integer of 2 to 5, preferably 2 or 3,

Specific aspects and preferred aspects of R are the same as those described in the general formula (1b).

The ratio of the structural unit represented by Formula (1) in all the structural units of the polymer P becomes like this. Preferably it is 3-40 mol%, More preferably, it is 3-30 mol%.

Structural unit represented by Formula (2) WHEREIN: R ^S is group containing only one (meth)acryloyl group. In one embodiment, in addition to the structural unit of Formula (1) containing two or more (meth)acryloyl groups, the polymer P contains the structural unit of Formula (2) containing only one acryloyl group. do. When the polymer P contains both of these structural units, it is possible to make the sensitivity and developability more highly compatible. In particular, in the design of a normal photosensitive resin composition, when the curability is increased to increase the sensitivity, the curing proceeds excessively and the developability tends to deteriorate. On the other hand, when the developability is improved, the curing tends to be insufficient. Therefore, it is preferable that the polymer P contains the structural unit represented by Formula (1) in combination, and the structural unit represented by Formula (2), and, thereby, can make both a sensitivity and developability compatible with favorable balance.

R ^S is, for example, group represented by the following formula (2a).

[Formula 13]

As mentioned above, although embodiment of this invention was described, these are illustrations of this invention, and various structures other than the above can also be employ|adopted.

In the formula (2a), X ¹⁰ is a divalent organic group, and R is a hydrogen atom or a methyl group.

The total number of carbon atoms of X ¹⁰ is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 10.

In the formula (2a), X ¹⁰ is a divalent organic group, and R is a hydrogen atom or a methyl group.

The total number of carbon atoms of X ¹⁰ is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 10.

As the divalent organic group of X ¹⁰ , for example, an alkylene group is preferable. A part of -CH ₂ - in this alkylene group may be an ether group (-O-). Although linear or branched form may be sufficient as an alkylene group, it is more preferable that it is linear.

As a divalent organic group of X10, More preferably, it is a C3 ^- C6 linear alkylene group. By appropriately selecting the number of carbon atoms of X ¹⁰ (chain length of X ¹⁰ ), the structural unit represented by the formula (2) is more easily involved in the crosslinking reaction, and the sensitivity can be increased.

^The divalent organic group (for example, an alkylene group) of X10 may be substituted by arbitrary substituents. As a substituent, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, etc. are mentioned.

Moreover, arbitrary contributions other than an alkylene group may be sufficient as the divalent organic group of X< ¹⁰ >. For example, a divalent contribution constituted by connecting one or more groups selected from an alkylene group, a cycloalkylene group, an arylene group, an ether group, a carbonyl group, a carboxy group, and the like may be acceptable.

When polymer P contains the structural unit represented by Formula (2), the ratio of the structural unit represented by Formula (2) in all the structural units of polymer P becomes like this. Preferably it is 5-40 mol%, More preferably, it is 10 ~30 mol%.

Moreover, when the polymer P contains the structural unit represented by Formula (1) and the structural unit represented by Formula (2), in the polymer P, the structural unit represented by Formula (1) and the structural unit represented by Formula (2) The total content is preferably 5 to 60 mol%, more preferably 10 to 50 mol%, still more preferably 10 to 40 mol%, based on all the structural units constituting the polymer P.

In addition, the content (ratio) of each structural unit contained in the polymer P is determined by the input amount (molar amount) of the raw material used when synthesizing the polymer, the amount of the raw material remaining after the synthesis, and various spectra (eg, IR spectrum, ¹ H -NMR spectrum, ¹³ C-NMR spectrum), the presence of a peak, peak area, etc. can be estimated/calculated.

The weight average molecular weights Mw of polymer P are, for example, 1000-20000, Preferably it is 2000-18000, More preferably, it is 3000-14000, More preferably, it is 3000-12000. By appropriately adjusting the weight average molecular weight, the sensitivity and solubility in an alkali developer can be adjusted.

Moreover, the dispersion degree (weight average molecular weight Mw/number average molecular weight Mn) of polymer P becomes like this. Preferably it is 1.0-5.0, More preferably, it is 1.0-4.0, More preferably, it is 1.0-3.0. By appropriately adjusting the degree of dispersion, the physical properties of the polymer P can be made homogeneous, which is preferable. In addition, these values can be calculated|required by gel permeation chromatography (GPC) measurement using polystyrene as a standard substance.

The glass transition temperature of polymer P becomes like this. Preferably it is 150-250 degreeC, More preferably, it is 170-230 degreeC. Polymer P has a comparatively high glass transition temperature mainly by including the structural unit represented by Formula (NB). This is preferable at the point that the pattern formed on the board|substrate can exist stably in manufacture of a liquid crystal display device or a solid-state image sensor. In addition, a glass transition temperature can be calculated|required by differential thermal analysis (DTA), for example.

(Compound having two or more (meth)acryloyl groups (polyfunctional (meth)acrylic compound))

The resin composition of this embodiment contains the compound which has two or more (meth)acryloyl groups. By including such a compound, alkali solubility of a resin composition is improved, and yellowing of a resin composition is reduced by extension, and it becomes possible to obtain the hardened|cured material excellent in transparency. A polyfunctional (meth)acryl compound becomes like this. Preferably it is 3-9 functional, More preferably, it is 3-6 functional. By mix|blending the (meth)acrylic compound of such a number of functional groups with a resin composition, the sensitivity of the resin composition obtained can be improved.

As a compound having two or more (meth)acryloyl groups used for the resin composition of the present embodiment (referred to as "polyfunctional (meth)acryl compound" in this specification), for example, the following formula (1b- Although the compound represented by p), the compound represented by Formula (1c-p), and the compound represented by Formula (1d-p) are mentioned, It is not limited to these. The definitions and specific aspects of k, R, X ¹ , X ¹ ' and X ² in Formula (1b-p) are the same as those in Formula (1b) described above. In addition, the definitions and specific aspects of k, R, X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ in Formula (1c-p) are the same as those in Formula (1c) described above. . Y in formulas (1b-p), (1c-p), and (1d-p) is a hydrogen atom, a (meth)acryloyl group, or a combination thereof. n in Formula (1d-p) is an integer of 2 or more, Preferably it is an integer of 2-5, More preferably, it is an integer of 2-3. R in the formula (1d-p) is the same as in the formula (1d) described above.

[Formula 14]

[Formula 15]

[Formula 16]

Although the compound of the following structures is mentioned as a specific example of the polyfunctional (meth)acryl compound represented by Formula (1b-p), It is not limited to these. In the following compounds, Y represents a hydrogen atom, a (meth)acryloyl group, or a combination thereof.

[Formula 17]

[Formula 18]

[Formula 19]

Although the following compounds are mentioned as a specific example of the polyfunctional (meth)acryl compound represented by Formula (1c-p), It is not limited to these.

[Formula 20]

[Formula 21]

[Formula 22]

(Compound having one (meth)acryloyl group)

The resin composition of this embodiment may contain the compound (referred to as "monofunctional (meth)acryl compound" in this specification) which has one (meth)acryloyl group. By including a monofunctional (meth)acrylic compound, the alkali solubility of the resin composition obtained improves, and yellowing is reduced by extension.

As a monofunctional (meth)acrylic compound used for the resin composition of this embodiment, the compound represented by the following formula (2a-m) is mentioned. In the formula (2a-m), the definitions of X ¹⁰ and R are the same as in the formula (2a).

[Formula 23]

As a specific example of the compound represented by Formula (2a-m), 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1, 4- cyclohexane dimethanol mono(meth)acrylate , 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl- 2-hydroxyethyl-phthalic acid etc. are mentioned.

The resin composition of this embodiment WHEREIN: The said polyfunctional (meth)acrylic compound has the peak area derived from the polyfunctional (meth)acrylic compound in the gel permeation chromatography (GPC) chart of the said resin composition, a polymer With respect to the peak area of P, it mix|blends in the quantity used as 5-150%, for example. The lower limit of the peak area derived from the polyfunctional (meth)acrylic compound with respect to the peak area of the polymer P is preferably 10% or more, more preferably 20% or more, still more preferably 30% or more. and even more preferably, 40% or more, and particularly preferably, 50% or more. The upper limit of the peak area derived from the polyfunctional (meth)acrylic compound with respect to the peak area of the polymer P is preferably 140% or less, more preferably 135% or less, still more preferably 130% or less. and even more preferably, 125% or less, and particularly preferably, 120% or less. The resin composition obtained by mix|blending a polyfunctional (meth)acrylic compound in the said range has the outstanding alkali solubility.

When a monofunctional (meth)acrylic compound is mix|blended with the resin composition of this embodiment, the peak derived from the monofunctional (meth)acrylic compound in the gel permeation chromatography (GPC) chart of the said resin composition The area is blended in an amount that is, for example, 5 to 60% with respect to the peak area of the polymer P. The lower limit of the peak area derived from the monofunctional (meth)acrylic compound with respect to the peak area of the polymer P is preferably 7% or more, more preferably 9% or more, still more preferably 10% or more. to be. The upper limit of the peak area derived from the monofunctional (meth)acrylic compound with respect to the peak area of the polymer P is preferably 55% or less, more preferably 50% or less, still more preferably 45% or less. to be. By mix|blending a monofunctional (meth)acrylic compound in the said range, while the resin composition obtained has the outstanding alkali solubility, heat discoloration resistance is improved.

The resin composition of this embodiment can make the alkali dissolution rate into 250 nm/s or more, for example by providing the said structure, Preferably, it can be 280 nm/s or more.

The resin composition of this embodiment contains an organic solvent typically, and is provided in the form of a liquid or a varnish. As an organic solvent, 1 type(s), or 2 or more types of a ketone type solvent, an ester type solvent, an ether type solvent, an alcohol type solvent, a lactone type solvent, a carbonate type solvent, etc. can be used.

Specific examples of the organic solvent include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, γ-butyrolactone, N-methylpyrrolidone and cyclohexanone. These may be used individually by 1 type, and may be used in combination of 2 or more type.

Although the usage-amount of organic solvent is not specifically limited, The density|concentration of a non-volatile component is 10-70 mass %, for example, Preferably it is used in the quantity so that it will be 15-60 mass %.

(Preparation of Polymer P)

Here, the manufacturing method of the above-mentioned polymer P is demonstrated.

Polymer P can be manufactured (synthesized) by arbitrary methods. Polymer P is, for example,

Step (I): a step of preparing a raw material polymer comprising a structural unit represented by the formula (NB) and a structural unit represented by the formula (MA); and

Step (II): The raw material polymer obtained in step (I) and a compound having a hydroxyl group and two or more (meth)acryloyl groups (hereinafter referred to as “polyfunctional (meth)acryl monomer”) are used as a basic catalyst reacted in the presence of to prepare a polymer P further comprising the structural unit represented by the formula (NB), the structural unit represented by the formula (1), and, in some cases, the structural unit represented by the formula (MA) can

When the polymer P further contains the structural unit represented by the formula (2), in the step (II), the raw material polymer obtained in the step (I), a polyfunctional (meth)acryl monomer and a hydroxyl group, and one ( A compound having a meth)acryloyl group (hereinafter referred to as "monofunctional (meth)acryl monomer") is reacted in the presence of a basic catalyst, the structural unit represented by the formula (NB), the structural unit represented by the formula (1) It can manufacture by the process of preparing polymer P further containing the structural unit represented by , and Formula (2), and the structural unit represented by Formula (MA) as the case may be.

When polymer P further contains the structural unit represented by Formula (3), in process (II), it is a structural unit represented by Formula (NB), a structural unit represented by Formula (1), and/or Formula (2) A process of treating the polymer with water in the presence of a base catalyst after preparing a polymer containing the structural unit represented by the structural unit and the structural unit represented by the formula (MA) is performed (Step (III)).

When polymer P contains a thioether group, such a polymer P can be manufactured by using the raw material polymer into which the thioether group was introduce|transduced in the process (II). Specifically, in the step (I), the raw material polymer containing a thioether group comprises a structural unit represented by the formula (NB), a structural unit represented by the formula (MA), and a raw material polymer containing a thioether group. obtained by manufacturing. The production of the raw material polymer into which the thioether group is introduced will be described in detail below.

In step (II), when both a polyfunctional (meth)acryl monomer and a monofunctional (meth)acryl monomer are used, the polyfunctional (meth)acryl monomer is first reacted with a raw material polymer, and in the obtained reaction mixture, It is preferable to react a functional (meth)acryl monomer.

(Process (I))

In the step (I), the step of preparing a raw material polymer including the structural unit represented by the formula (NB) and the structural unit represented by the formula (MA) is a monomer represented by the formula (NBm) and maleic anhydride A step of obtaining the target raw material polymer by polymerization (addition polymerization) is included. In addition, the definitions of R ¹ , R ² , R ³ and R ⁴ and a ₁ of the formula (NBm) are the same as those of the formula (NB). It is the same also about a preferable aspect.

In the step (I), when preparing a raw material polymer having a thioether group introduced therein, such a raw material polymer is polymerized (addition) of a monomer represented by formula (NBm) and maleic anhydride in the presence of a thiol group-containing compound. polymerization). The thioether group introduced into the raw material polymer obtained is a group derived from the thiol group of this thiol group-containing compound.

[Formula 24]

Examples of the monomer represented by the formula (NBm) include norbornene, norbornadiene, bicyclo[2.2.1]-hept-2-ene (common name: 2-norbornene), and 5-methyl-2-norbornene. , 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2-norbornene, 5-allyl-2-norbornene, 5- (2 -Propenyl)-2-norbornene, 5-(1-methyl-4-pentenyl)-2-norbornene, 5-ethynyl-2-norbornene, 5-benzyl-2-norbornene, 5- phenethyl-2-norbornene, 2-acetyl-5-norbornene, 5-norbornene-2-methyl carboxylate, 5-norbornene-2,3-dicarboxylic acid anhydride, and the like. In the case of superposition|polymerization, only 1 type may be used for the monomer represented by Formula (NBm), and it may use it in combination of 2 or more type.

As the thiol group-containing compound used to prepare the raw material polymer into which the thioether group is introduced, it is preferable to use a thiol group-containing compound having two or more thiol groups, in other words, a thiol group-containing compound having two or more functionalities, trifunctional to hexafunctional It is more preferable that it is a thiol group containing compound. By using such a thiol group-containing compound, the sensitivity of the obtained polymer P can be improved.

Specific examples of the thiol group-containing compound include compounds represented by the following formulas (s-1) to (s-20), but are not limited thereto. A thiol group containing compound may be used individually by 1 type, and may mix and use 2 or more types.

[Formula 25]

Although it does not limit about the method of superposition|polymerization of the monomer represented by Formula (NBm), and maleic anhydride, Radical polymerization using a radical polymerization initiator is preferable. As a polymerization initiator, an azo compound, an organic peroxide, etc. can be used, for example.

Specifically as the azo compound, azobisisobutyronitrile (AIBN), dimethyl 2,2'-azobis(2-methylpropionate), 1,1'-azobis(cyclohexanecarbonitrile) (ABCN) etc. are mentioned.

Examples of the organic peroxide include hydrogen peroxide, di-tert-butyl peroxide (DTBP), benzoyl peroxide (benzoyl peroxide, BPO), and methyl ethyl ketone peroxide (MEKP).

About a polymerization initiator, only 1 type may be used and may be used in combination of 2 or more type.

As a solvent used for a polymerization reaction, organic solvents, such as diethyl ether, tetrahydrofuran, toluene, methyl ethyl ketone, can be used, for example. A single solvent may be sufficient as a polymerization solvent, and a mixed solvent may be sufficient as it.

In the synthesis of the raw material polymer containing the structural unit represented by the formula (NB) and the structural unit represented by the formula (MA), the monomer represented by the formula (NBm), maleic anhydride, and a polymerization initiator are dissolved in a solvent and put into a reaction vessel It is carried out by heating and advancing addition polymerization after that. The heating temperature is, for example, 50 to 80°C, and the heating time is, for example, 5 to 20 hours.

It is preferable that the molar ratio of the monomer represented by Formula (NBm) at the time of inject|throwing-in to a reaction container, and maleic anhydride is 0.5:1-1:0.5. From the viewpoint of molecular structure control, the molar ratio is preferably 1:1.

By such a process, a "raw material polymer" can be obtained.

The raw material polymer may be any of a random copolymer, an alternating copolymer, a block copolymer, a periodic copolymer, and the like. They are typically random or alternating copolymers. In addition, in general, maleic anhydride is known as a monomer with strong alternating copolymerizability.

The synthesis of a raw material polymer into which a thioether group is introduced, including a structural unit represented by Formula (NB), a structural unit represented by Formula (MA), and a thioether group, is a monomer represented by Formula (NBm), maleic anhydride and dissolving the polymerization initiator in a solvent and putting it into a reaction vessel, followed by heating and adding the above-described thiol group-containing compound dropwise to proceed addition polymerization. The heating temperature is, for example, 50 to 80°C, and the heating time is, for example, 5 to 20 hours.

It is preferable that the molar ratio of the monomer represented by Formula (NBm) at the time of inject|throwing-in to a reaction container, and maleic anhydride is 0.5:1-1:0.5. From the viewpoint of molecular structure control, the molar ratio is preferably 1:1.

In addition, from the viewpoint of the thioether group content in the raw material polymer into which the thioether group is introduced, and the molecular weight control of the raw material polymer, the sum of the monomers represented by the formula (NBm) and maleic anhydride when introduced into the reaction vessel With respect to the molar amount, the input amount of the thiol group-containing compound is preferably 0.5 to 10 mol%, particularly preferably 1 to 8 mol%, and more preferably 2 to 6 mol%.

Moreover, you may perform the process of removing low molecular weight components, such as an unreacted monomer, an oligomer, and a polymerization initiator, which remain|survived after the synthesis|combination of a raw material polymer.

Specifically, the synthesized raw material polymer and the organic phase containing the low molecular weight component are concentrated, and then mixed with an organic solvent such as tetrahydrofuran (THF) to obtain a solution. And this solution is mixed with poor solvents, such as methanol, and a monomer is precipitated. The purity of the raw material polymer can be increased by filtering and drying this precipitate.

Polymer P of the present embodiment is produced by using the raw material polymer obtained in step (I) in the following steps (II) and (III). In the following description, as the raw material polymer obtained in step (I), the case where the raw material polymer comprising the structural unit represented by the formula (NB) and the structural unit represented by the formula (MA) is used is described. Even when a raw material polymer is used, the same method can be used, and the polymer P obtained in this case contains a thioether group.

(Process (II))

By reacting the raw material polymer obtained in step (I) with a polyfunctional (meth)acryl monomer, and optionally a monofunctional (meth)acryl monomer in the presence of a basic catalyst, represented by the formula (MA) contained in the raw material polymer When a part of a structural unit is ring-opened and the structural unit represented by Formula (1) and a monofunctional (meth)acryl monomer are used, the structural unit represented by Formula (2) is formed, and the structural unit represented by Formula (NB) , and a structural unit represented by Formula (1), and a structural unit represented by Formula (2) (when a monofunctional (meth)acryl monomer is used), and optionally including a structural unit represented by Formula (MA) Polymer P is obtained.

More specifically, first, a solution in which a raw material polymer is dissolved in a suitable organic solvent is prepared. Examples of the organic solvent include methyl ethyl ketone (MEK), propylene glycol monomethyl ether acetate (PGMEA), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), tetrahydrofuran (THF), and the like. Although a single solvent or a mixed solvent can be used, it is not limited to these, Various organic solvents used in the synthesis|combination of an organic compound or a polymer|macromolecule can be used.

Next, a polyfunctional (meth)acryl monomer is added to the above solution. Also, a basic catalyst is added. And the solution is mixed suitably to make a uniform solution, and the polymer containing at least the structural unit of Formula (NB) and the structural unit of Formula (1) is obtained (step (II-i)).

As a polyfunctional (meth)acryl monomer which can be used here, for example, the compound represented by the above-mentioned formula (1b-p), the compound represented by the formula (1c-p), and the compound represented by the formula (1d-p) In this case, a compound in which Y is a hydrogen atom is exemplified.

Next, by reacting a monofunctional (meth)acryl monomer with the polymer obtained in step (II-i) in the presence of a basic catalyst, at least the structural unit of Formula (NB), the structural unit of Formula (1), and Formula ( A polymer containing the structural unit of 2) can be obtained (Step (II-ii)).

Although either one of a process (II-i) and a process (II-ii) may be implemented, it is preferable to implement the process (II-i) preferably. When performing both the process (II-i) and the process (II-ii), it is preferable to implement the process (II-ii) following the process (II-i).

(Process (III))

When implementing the step (III), a step of treating the polymer obtained in the step (II) with water in the presence of a basic catalyst is used. By the step (III), the structural unit represented by the formula (MA) contained in the polymer obtained in the step (II) is ring-opened, and the structural unit represented by the formula (3) is formed, the structural unit represented by the formula (NB); Polymer P containing the structural unit represented by Formula (1) and/or the structural unit represented by Formula (2), and the structural unit represented by Formula (3) can be manufactured. When a part of the structural unit represented by the formula (MA) is ring-opened and a part of the structural unit of the formula (MA) remains without ring-opening, the polymer P is the formula (NB), the formulas (1) and (2) ( In addition to the structural unit of Formula (3) and the structural unit of Formula (3), when a monofunctional (meth)acryl monomer is used in process (II), the structural unit represented by Formula (MA) is included.

Examples of the basic catalyst used in step (III) include amine compounds such as triethylamine, pyridine and dimethylaminopyridine, or nitrogen-containing heterocyclic compounds.

In the step (III), water is added to the reaction system containing the polymer obtained in the step (II), and the resulting reaction solution is preferably heated at 60 to 80° C. for about 0.25 to 6 hours to be incorporated into the polymer. The structural unit of Formula (MA) used is ring-opened, and the structural unit represented by Formula (3) is produced|generated. As the basic catalyst, the catalyst remaining in the reaction system obtained in step (II) can be used as it is. Therefore, it is preferable to carry out the step (III) by further adding water to the reaction mixture as it is, without performing any post-treatment to the reaction mixture obtained in the step (II).

(Preparation of resin composition)

The resin composition of this embodiment can be produced by mixing the said component by a well-known method. The resin composition of this embodiment is used as a resin material of the photosensitive resin composition demonstrated below.

(Photosensitive resin composition)

The photosensitive resin composition of this embodiment contains the polymer P mentioned above, the compound (polyfunctional (meth)acryl compound) which has two or more (meth)acryloyl groups, and a photosensitive agent. That is, the photosensitive resin composition of this embodiment contains the resin composition of this embodiment mentioned above, and a photosensitive agent. Each component is demonstrated below.

Polymer P and polyfunctional (meth)acryl compound used for the photosensitive resin composition of this embodiment are the same as those mentioned above.

A photoradical polymerization initiator is mentioned as a photosensitive agent used for the photosensitive resin composition of this embodiment. As the photoradical polymerization initiator, a known compound can be used, for example, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone , 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1- one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one, 2-methyl-1-(4- Methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-(dimethylamino) alkylphenone compounds such as -2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; benzophenone-based compounds such as benzophenone, 4,4'-bis(dimethylamino)benzophenone, and 2-carboxybenzophenone; benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Thioxanthones such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, and 2,4-diethylthioxanthone compound; 2-(4-Methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s- Triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(tri halomethylated triazine-based compounds such as chloromethyl)-s-triazine; 2-Trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuryl)vinyl]-1,3 Halomethylated oxadiazole compounds such as ,4-oxadiazole, 4-oxadiazole, and 2-trichloromethyl-5-furyl-1,3,4-oxadiazole; 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl) -4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5' -biimidazole type compounds, such as tetraphenyl-1,2'- biimidazole; 1,2-Octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H -carbazol-3-yl]-1-(O-acetyloxime) and other oxime ester compounds; titanocene compounds such as bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium; benzoic acid ester compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; acridine-based compounds such as 9-phenylacridine; and the like. A photoradical polymerization initiator may be used individually by 1 type, and may be used in combination of 2 or more type.

A photoradical polymerization initiator is the quantity of 1-20 mass parts with respect to 1000 mass parts of polymer P, Preferably, it is used in the quantity of 3-10 mass parts.

The photosensitive resin composition of this embodiment has the outstanding alkali solubility while having high sensitivity in a photolithographic process by including the said component. Therefore, the photosensitive resin composition is equipped with the outstanding developability and the outstanding processability in the photolithographic method. Moreover, since yellowing of the photosensitive resin composition is suppressed, the article obtained by hardening the said photosensitive resin composition has transparency.

As an aspect, the photosensitive resin composition may also contain a coloring agent. By including a coloring agent, it can use suitably as a forming material of the color filter of a liquid crystal display device or a solid-state image sensor. As the colorant, various pigments or dyes can be used.

As the pigment, an organic pigment or an inorganic pigment can be used.

Examples of the organic pigment include azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, perinone pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, thioindigo pigments, Anthraquinone pigments, quinophthalone pigments, metal complex pigments, diketopyrrolopyrrole pigments, xanthene pigments, pyromethene pigments, dye lake pigments, etc. can be used.

Examples of inorganic pigments include white and constitutional pigments (titanium oxide, zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.), oil-colored pigments (chromium yellow, cadmium-based, chromium vermillion, nickel titanium, chromium titanium, Yellow iron oxide, bengala, zinc chromate, lead, ultramarine blue, royal blue, cobalt blue, chromium green, chromium oxide, bismuth vanadate, etc.), brilliance pigments (pearl pigments, aluminum pigments, bronze pigments, etc.), fluorescent Pigments (zinc sulfide, strontium sulfide, strontium aluminate, etc.) can be used.

As dye, the well-known dye described in Unexamined-Japanese-Patent No. 2003-270428, Unexamined-Japanese-Patent No. 9-171108, Unexamined-Japanese-Patent No. 2008-50599, etc. can be used, for example.

When the photosensitive resin composition contains a coloring agent, the photosensitive resin composition may contain only 1 type and may contain 2 or more types of coloring agents.

As the colorant (particularly pigment), one having an appropriate average particle diameter can be used depending on the purpose or use. In particular, when transparency such as a color filter is required, a small average particle diameter of 0.1 μm or less is preferable. When hiding properties such as etc. are required, a large average particle diameter of 0.5 µm or more is preferable.

The colorant may be subjected to a surface treatment such as a rosin treatment, a surfactant treatment, a resin-based dispersant treatment, a pigment derivative treatment, an oxide film treatment, a silica coating, or a wax coating depending on the purpose or use.

When the photosensitive resin composition contains a colorant, the amount thereof may be appropriately set according to the purpose or use, but from the viewpoint of coexistence of the color concentration and dispersion stability of the colorant, etc., the total non-volatile components (components excluding the solvent) of the photosensitive resin composition , Preferably it is 3-70 mass %, More preferably, it is 5-60 mass %, More preferably, it is 10-50 mass %.

As an aspect, the photosensitive resin composition may contain a light-shielding agent. By including a light-shielding agent, it can use suitably as a formation material of the black matrix of a liquid crystal display device or a solid-state image sensor.

As a light-shielding agent, a well-known light-shielding agent in particular can be used without restriction|limiting. For example, black pigments, such as carbon black, bone black, graphite, iron black, and titanium black, can be used as a light-shielding agent.

When the photosensitive resin composition contains a light-shielding agent, the photosensitive resin composition may contain only 1 type of light-shielding agents, and may contain it 2 or more types.

When the photosensitive resin composition contains a light-shielding agent, the amount thereof may be appropriately set according to the purpose or use. To that, Preferably it is 3-70 mass %, More preferably, it is 5-60 mass %, More preferably, it is 10-50 mass %.

The photosensitive resin composition typically contains a solvent. As the solvent, an organic solvent is preferably used. Specifically, one or two or more of ketone-based solvents, ester-based solvents, ether-based solvents, alcohol-based solvents, lactone-based solvents, carbonate-based solvents, and the like can be used.

Examples of the solvent include propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate, methyl isobutyl carbinol (MIBC), gamma butyrolactone (GBL), N -Methylpyrrolidone (NMP), methyl-n-amylketone (MAK), diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclo hexanone, or a mixture thereof.

Although the usage-amount of a solvent is not specifically limited, The density|concentration of a non-volatile component is 10-70 mass %, for example, Preferably it is used in the quantity so that it will be 15-60 mass %.

In one embodiment, the photosensitive resin composition may include a crosslinking agent.

The crosslinking agent is not particularly limited as long as it can crosslink the polymer by the action of active chemical species generated from the photopolymerization initiator (that can chemically bond with the polymer).

The crosslinking agent may not chemically bond only with the polymer, but may react with each other to form a bond.

The crosslinking agent is, for example, preferably a polyfunctional compound having two or more polymerizable double bonds in one molecule, and more preferably a polyfunctional (meth)acrylic compound having two or more (meth)acryloyl groups in one molecule. (However, the crosslinking agent does not correspond to the above-mentioned polymer). It is preferable to use the crosslinking agent which has a crosslinkable group (polymerizable double bond) and the same kind of crosslinkable group which a polymer has from points, such as uniform sclerosis|hardenability and further improvement of a sensitivity.

Although there is no upper limit in particular of the functional number (the number of polymerizable double bonds) per molecule of crosslinking agent, For example, it is 8 or less, Preferably it is 6 or less.

Specific examples of the crosslinking agent include the following.

Ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di (meth)acrylate, hexanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, bisphenol A alkylene oxide di(meth)acrylate, bisphenol F alkylene oxide di(meth) Acrylate, trimethylol propane tri (meth) acrylate, ditrimethylol propane tetra (meth) acrylate, glycerin tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol Penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide addition trimethylol propane tri (meth) acrylate, ethylene oxide addition ditrimethylol propane tetra (meth) acrylate, ethylene Oxide addition pentaerythritol tetra (meth) acrylate, ethylene oxide addition dipentaerythritol hexa (meth) acrylate, propylene oxide addition trimethylol propane tri (meth) acrylate, propylene oxide addition ditrimethylol propane Tetra (meth) acrylate, propylene oxide addition pentaerythritol tetra (meth) acrylate, propylene oxide addition dipentaerythritol hexa (meth) acrylate, ε-caprolactone addition trimethylolpropane tri (meth) acrylate , ε-caprolactone addition ditrimethylolpropanetetra(meth)acrylate, ε-caprolactone addition pentaerythritoltetra(meth)acrylate, ε-caprolactone addition dipentaerythritol hexa(meth)acrylate, etc. of polyfunctional (meth)acrylates.

Ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol Divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether, trimethylol propane trivinyl ether, ditrimethylol propane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide addition trimethylol propane trivinyl ether, ethylene oxide addition ditrimethylol propane Polyfunctional vinyl ethers, such as tetravinyl ether, ethylene oxide addition pentaerythritol tetravinyl ether, and ethylene oxide addition dipentaerythritol hexavinyl ether.

(meth)acrylic acid 2-vinyloxyethyl, (meth)acrylic acid 3-vinyloxypropyl, (meth)acrylic acid 1-methyl-2-vinyloxyethyl, (meth)acrylic acid 2-vinyloxypropyl, (meth)acrylic acid 4- Vinyloxybutyl, (meth)acrylic acid 4-vinyloxycyclohexyl, (meth)acrylic acid 5-vinyloxypentyl, (meth)acrylic acid 6-vinyloxyhexyl, (meth)acrylic acid 4-vinyloxymethylcyclohexylmethyl, (meth)acrylic acid ) acrylic acid p-vinyloxymethylphenylmethyl, (meth)acrylic acid 2-(vinyloxyethoxy)ethyl, (meth)acrylic acid 2-(vinyloxyethoxyethoxyethoxy)ethyl, containing vinyl ether groups (meth) Acrylic acid esters.

Ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexanediol Diallyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkylene oxide diallyl ether, trimethylol propane triallyl ether, ditrimethylol propane tetraallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, ethylene oxide addition trimethylol propane triallyl ether, ethylene oxide addition ditrimethylol propane Polyfunctional allyl ethers, such as tetraallyl ether, ethylene oxide addition pentaerythritol tetraallyl ether, and ethylene oxide addition dipentaerythritol hexaallyl ether.

Allyl group-containing (meth)acrylic acid esters, such as (meth)acrylic acid allyl.

Tri (acryloyloxyethyl) isocyanurate, tri (methacryloyloxyethyl) isocyanurate, alkylene oxide addition tri (acryloyloxyethyl) isocyanurate, alkylene oxide addition tri ( Polyfunctional (meth)acryloyl group containing isocyanurates, such as methacryloyloxyethyl) isocyanurate.

Polyfunctional allyl group-containing isocyanurates, such as triallyl isocyanurate.

Polyfunctional isocyanates, such as tolylene diisocyanate, isophorone diisocyanate, and xylylene diisocyanate, (meth)acrylic acid 2-hydroxyethyl, (meth)acrylic acid 2-hydroxy Polyfunctional urethane (meth)acrylates obtained by reaction with hydroxyl-containing (meth)acrylic acid esters, such as propyl.

Polyfunctional aromatic vinyls, such as divinylbenzene.

Among them, trifunctional (meth)acrylates such as trimethylolpropane tri(meth)acrylate and pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and ditrimethylolpropanetetra 6 functional (meth)acrylates, such as tetrafunctional (meth)acrylates, such as (meth)acrylate, and dipentaerythritol hexa(meth)acrylate, are preferable.

When the photosensitive resin composition contains a crosslinking agent, the photosensitive resin composition may contain only 1 type and may contain 2 or more types of crosslinking agents. When the photosensitive resin composition contains a crosslinking agent, what is necessary is just to set the quantity suitably according to the objective and a use. As an example, the quantity of a crosslinking agent is 30-70 mass parts normally with respect to 100 mass parts of polymer P, Preferably it is about 40-60 mass parts.

The photosensitive resin composition may contain a filler, a binder resin other than the above-mentioned polymer, an acid generator, a heat resistance improver, a developing aid, a plasticizer, a polymerization inhibitor, an ultraviolet absorber, an antioxidant, a gloss remover, an antifoaming agent, You may contain components, such as a leveling agent, surfactant, antistatic agent, a dispersing agent, a slip agent, a surface modifier, a thixotropic agent, a thixotropic auxiliary agent, a silane coupling agent, and a polyhydric phenol compound.

(Film, color filter, black matrix, liquid crystal display and solid-state image sensor)

A film with a pattern can be obtained by forming a film using the photosensitive resin composition mentioned above, exposing and developing the film, and forming a pattern. This film is applied to a color filter, a black matrix, etc. That is, a color filter can be obtained by forming a pattern using the photosensitive resin composition containing a coloring agent. Moreover, a black matrix can be obtained by forming a pattern using the photosensitive resin composition containing a light-shielding agent. And the liquid crystal display device and solid-state image sensor provided with a color filter and a black matrix can be manufactured.

A typical procedure for forming a pattern is described.

(Formation of photosensitive resin film)

For example, first, the photosensitive resin film is obtained by apply|coating said photosensitive resin composition on arbitrary board|substrates, and drying it as needed.

The substrate to which the composition is applied is not particularly limited. For example, a glass substrate, a silicon wafer, a ceramic substrate, an aluminum substrate, a SiC wafer, a GaN wafer, a copper clad laminated board etc. are mentioned.

The substrate may be a raw substrate or a substrate having electrodes and elements formed on the surface thereof. It may be surface-treated for the improvement of adhesiveness.

The coating method of the photosensitive resin composition is not specifically limited. Spin coating using a spinner, spray coating using a spray coater, immersion, printing, roll coating, inkjet method, etc. can carry out.

Drying of the photosensitive resin composition apply|coated on the board|substrate is typically performed by heat-processing with a hot plate, hot air, oven, etc. Heating temperature is 80-140 degreeC normally, Preferably it is 90-120 degreeC. Moreover, the time of a heating is 30 to 600 second normally, Preferably it is about 30 to 300 second.

The film thickness of the photosensitive resin film is not specifically limited, Although it may adjust suitably according to the pattern to be finally obtained, Usually, it is 0.5-10 micrometers, Preferably it is 1-5 micrometers. In addition, a film thickness can be adjusted with content of the solvent in the photosensitive resin composition, the application|coating method, etc.

(exposure)

Exposure is typically performed by irradiating an actinic ray to the photosensitive resin film through an appropriate photomask.

Examples of actinic rays include X-rays, electron beams, ultraviolet rays, and visible rays. In terms of wavelength, light of 200 to 500 nm is preferable. It is preferable that a light source is g line|wire, h line|wire, or i line|wire of a mercury lamp from the point of the resolution and handling property of a pattern, and especially i line|wire is preferable. Moreover, you may mix and use two or more light rays. As the exposure apparatus, a contact aligner, a mirror projection aligner, or a stepper is preferable.

Although what is necessary is just to adjust the light quantity of exposure suitably with the quantity etc. of the photosensitive agent in the photosensitive resin film, it is about 100-500 mJ/cm< ² >, for example.

In addition, you may heat the photosensitive resin film again after exposure as needed (post-exposure heating: Post Exposure Bake). The temperature is, for example, 70 to 150°C, preferably 90 to 120°C. Moreover, time is 30-600 second, for example, Preferably it is 30-300 second. By heating after exposure, the reaction by the radical generated from the photoradical polymerization initiator is accelerated|stimulated, and hardening reaction is accelerated|stimulated further.

(phenomenon)

By developing the exposed photosensitive resin film with a suitable developing solution, obtaining a pattern and the board|substrate provided with a pattern can be manufactured.

In a developing process, using a suitable developing solution, for example, it can develop using methods, such as an immersion method, the puddle method, and the rotary spray method. By development, the exposed part (in the case of a positive type) or an unexposed part (in the case of a negative type) of the photosensitive resin film is eluted and removed, and a pattern is obtained.

The developer that can be used is not particularly limited. For example, an aqueous alkali solution or an organic solvent can be used.

Specific examples of the aqueous alkali solution include (i) an inorganic aqueous alkali solution such as sodium hydroxide, sodium carbonate, sodium silicate, and ammonia, (ii) an organic amine aqueous solution such as ethylamine, diethylamine, triethylamine, and triethanolamine, ( iii) aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide; and the like.

Specific examples of the organic solvent include ketone solvents such as cyclopentanone, ester solvents such as propylene glycol monomethyl ether acetate (PGMEA) and butyl acetate, and ether solvents such as propylene glycol monomethyl ether. and the like.

Water-soluble organic solvents, such as methanol and ethanol, surfactant, etc. may be added to a developing solution, for example.

In this embodiment, it is preferable to use aqueous alkali solution as a developing solution, and it is more preferable to use tetramethylammonium hydroxide, sodium carbonate aqueous solution, or potassium hydroxide aqueous solution.

The density|concentration of aqueous alkali solution becomes like this. Preferably it is 0.1-10 mass %, More preferably, it is 0.2-5 mass %.

Although obtaining a pattern/a board|substrate provided with a pattern can be manufactured by the above process, you may perform various processing after image development.

For example, after development, the pattern and the substrate may be washed with a rinse solution. As a rinse liquid, distilled water, methanol, ethanol, isopropanol, propylene glycol monomethyl ether etc. are mentioned, for example. These may be used independently and may be used in combination of 2 or more type.

Moreover, you may make it harden|harden enough by heating the obtained pattern. Heating temperature is 150-400 degreeC typically, Preferably it is 160-300 degreeC, More preferably, it is 200-250 degreeC. Although heating time is not specifically limited, For example, it exists in the range for 15 to 300 minutes. This heat treatment can be performed by a hot plate, an oven, a temperature rising type oven in which a temperature program can be set, or the like. As atmospheric gas at the time of heat processing, air may be sufficient, and inert gas, such as nitrogen and argon, may be sufficient. Moreover, you may heat under reduced pressure.

An example of the structure of a liquid crystal display device and/or a solid-state image sensor provided with a color filter and/or a black matrix is typically shown in FIG.

On the substrate 10 , a black matrix 11 and a color filter 12 are formed. In addition, a protective film 13 and a transparent electrode layer 14 are provided on the black matrix 11 and the color filter 12 .

The board|substrate 10 is comprised with the material which passes light normally, For example, polyester, polycarbonate, polyolefin, polysulfone, the polymer of a cyclic olefin other than glass, etc. are comprised. The substrate 10 may have been subjected to corona discharge treatment, ozone treatment, chemical treatment, or the like as needed.

The substrate 10 is preferably made of glass.

The black matrix 11 is comprised by the hardened|cured material of the photosensitive resin composition containing a light-shielding agent, for example.

As the color filter 12, three colors of red, green, and blue exist normally. The color filter 12 is comprised by the hardened|cured material of the photosensitive resin composition containing the coloring agent according to each color.

As mentioned above, although embodiment of this invention was described, these are illustrations of this invention, and various structures other than the above are employable. In addition, this invention is not limited to embodiment mentioned above, A deformation|transformation, improvement, etc. within the range which can achieve the objective of this invention are contained in this invention.

Example

EMBODIMENT OF THE INVENTION Embodiment of this invention is described in detail based on an Example and a comparative example. In addition, this invention is not limited to an Example.

About the compound used in an Example, it may represent with the following abbreviation|symbol or a brand name.

MA: maleic anhydride

NB: 2-norbornene

·MEK: methyl ethyl ketone

4-HBA: 4-hydroxybutyl acrylate

・A-TMM-3LM-N: A mixture of the following two compounds, the amount of the compound on the left in the mixture based on gas chromatography measurement is about 57% (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[Formula 26]

・A-9550: A mixture of the following two compounds, the amount of the compound on the left in the mixture evaluated from the hydroxyl value is about 50% (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[Formula 27]

-Viscoat #802: A mixture of tripentaerythritol acrylates, mono- and dipentaerythritol acrylates, and polypentaerythritol acrylates represented by the following formulas (manufactured by Osaka Yuki Chemical Co., Ltd.)

[Formula 28]

n=1: 10-20%

n=2: 55-65%

n=3: 5-15%

<Synthesis of raw material polymer>

(Synthesis of Raw Polymer 1)

In an appropriately sized reaction vessel equipped with a stirrer and cooling tube, 588.36 g (6.0 moles) of maleic anhydride, 564.90 g (6.0 moles) of 2-norbornene, and dimethyl2,2'-azobis(2-methyl propionate) 55.26 g (0.24 mol) was weighed in. These were dissolved in a mixed solvent comprising 1716.8 g of methyl ethyl ketone and 188.3 g of toluene to prepare a solution.

This solution was vented with nitrogen for 30 minutes to remove oxygen, then heated at a temperature of 65°C with stirring for 1.5 hours, and then heated at 80°C for 6 hours to obtain maleic anhydride and 2-norbornene. It was made to superpose|polymerize, and the polymerization solution was produced.

A white solid was precipitated by dripping the polymerization solution obtained above to 14230.2 g of methanol. The obtained white solid was further washed with 3557.5 g of methanol and then vacuum dried at a temperature of 120° C., thereby comprising a structural unit derived from 2-norbornene and a structural unit derived from maleic anhydride (raw material polymer 1) ) to obtain 1027.2 g.

As a result of measuring the obtained polymer using gel permeation chromatography (GPC), the weight average molecular weight Mw was 7236, and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 1.83.

(Synthesis of Raw Polymer 2)

In a reaction vessel equipped with a stirrer and a cooling tube and a dropping funnel, 602.56 g of a 75% toluene solution of 2-norbornene (451.92 g of 2-norbornene, 4.8 mol), maleic anhydride (MAN, 470.69 g, 4.8 mol) and 2281.74 g of methyl ethyl ketone (MEK) were added and stirred and dissolved. Next, after removing dissolved oxygen in the system by nitrogen bubbling, heating was performed and when the internal temperature reached 80°C, 2,2'-azobisisobutyrate dimethyl (manufactured by Wako Pure Chemical Industries, Ltd., trade name) : V-601, 44.21 g, 0.19 mol) and pentaerythritol tetrakis (3-mercaptopropionate) (PEMP (a thiol group-containing compound of the above formula (s-2)), 93.82 g, 0.19 mol) A solution of 193.4 g of MEK was added over 1 hour. Then, it was made to react at 80 degreeC for 7 hours more. Then, the reaction mixture was cooled to room temperature. White solid was precipitated by dripping the polymerization solution obtained above to 3686.4 g of methanol. The obtained white solid was further washed with 3686.4 g of methanol and then vacuum dried at a temperature of 120° C. to contain a structural unit derived from 2-norbornene, a structural unit derived from maleic anhydride, and a thioether group. 910.1 g of polymer (raw material polymer 2) was obtained.

As a result of measuring the obtained polymer using gel permeation chromatography (GPC), the weight average molecular weight Mw was 3500, and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 1.62.

<Preparation of resin composition>

The resin composition containing the polymer P and the polyfunctional (meth)acrylic compound was produced using the following method.

(Preparation Example 1)

Polymer P1 was prepared in which the MA unit of the raw material polymer 1 was ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water. Hereinafter, the detail is demonstrated.

First, 99.71 g of MEK was added to 60.00 g of raw material polymer 1 (0.312 mol in terms of MA) to prepare a solution. Next, 38.75 g of A-TMM-3LM-N was added to this solution, and 18.00 g (0.178 mol) of triethylamine was added after that, and it was made to react at the temperature of 70 degreeC for 2 hours. Furthermore, 56.27 g (0.390 mol) of 4-HBA was added after that, and it was made to react at the temperature of 70 degreeC for 4 hours, and the reaction solution was produced.

Then, without post-treatment of the obtained reaction solution, water 6.00 g (0.333 mol) was added to this reaction solution, and it was made to react at 70 degreeC for 0.5 hour.

The aqueous phase was removed from the reaction solution by diluting the obtained reaction solution with MEK and treating with an aqueous formic acid solution and an aqueous citric acid solution. Thereafter, the polymer was purified by the following procedure.

· The polymer was reprecipitated with an excess of toluene.

- The operation of washing the polymer powder obtained by reprecipitation with an excess amount of toluene was repeated twice.

- Operation of washing the polymer powder after washing|cleaning the said 2 times with excess water was performed 3 times.

- The obtained reaction product was dried at 40 degreeC for 12 hours.

As described above, 60.20 g of polymer P1 obtained by ring-opening the structural unit derived from maleic anhydride in the raw material polymer with A-TMM-3LM-N, 4-HBA and water was obtained.

(Preparation Example 2)

A resin mixture containing the polymer P2 in which the MA unit of the raw material polymer 1 was ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water was prepared. Hereinafter, the detail is demonstrated.

First, 99.71 g of MEK was added to 60.00 g of raw material polymer 1 (0.312 mol in terms of MA) to prepare a solution. Next, 38.75 g of A-TMM-3LM-N was added to this solution, and 18.00 g (0.178 mol) of triethylamine was added after that, and it was made to react at the temperature of 70 degreeC for 2 hours. Furthermore, 56.27 g (0.390 mol) of 4-HBA was added after that, and it was made to react at the temperature of 70 degreeC for 4 hours, and the reaction solution was produced.

Then, without post-treatment of the obtained reaction solution, water 6.00 g (0.333 mol) was added to this reaction solution, and it was made to react at 70 degreeC for 0.5 hour.

The aqueous phase was removed from the reaction solution by diluting the obtained reaction solution with MEK and treating with an aqueous formic acid solution and an aqueous citric acid solution. In addition, liquid-liquid extraction and then solvent substitution were performed in the following procedure.

- Liquid-liquid extraction: After removing the aqueous phase from the reaction solution by diluting the reaction solution with MEK, then adding water and treating it, the same operation was performed once more.

- Solvent substitution: The solvent was removed at 50 degreeC under reduced pressure using the rotary evaporator for the obtained reaction mixture. It was confirmed that the solid content concentration of the polymer solution was 27±2 mass % as measured by a heat-drying moisture meter, and the solvent removal operation was stopped. Then, PGMEA was added so that solid content concentration might be set to 18 mass %, and it mixed until it became uniform. In the same operation, the solvent is removed at 50°C under reduced pressure, the solid content concentration is adjusted to 27±2 mass% by measurement with a heat-drying moisture meter, and PGMEA is further added so that the solid content concentration is 18 mass%, uniformly The operation of mixing until dry was repeated two more times. Then, solvent removal or PGMEA was added so that solid content concentration might be set to 30±3 mass %, and operation of stirring was performed until it became uniform. By the above operation, the solvent used for the reaction is removed, and the solvent is replaced with PGMEA.

As described above, the structural unit derived from maleic anhydride in the raw material polymer is ring-opened with A-TMM-3LM-N, 4-HBA and water, and the remaining (free) A-TMM-3LM-N. And a resin mixture (resin composition) 2 containing residual (free) 4-HBA was obtained.

The obtained resin composition 2 was analyzed by gel permeation chromatography, and the amount of polymer P2, free polyfunctional (meth)acrylic compound and free monofunctional (meth)acrylic compound contained in the composition, and the weight average molecular weight of polymer P2 and Polydispersity was measured. A result is shown in Table 1. In addition, the amount of the free (meth)acrylic compound is expressed as a ratio (%) of the peak area of the free (meth)acrylic compound to the peak area of the polymer P in the gel permeation chromatography (GPC) chart of the resin mixture. .

In addition, the measurement conditions of the gel permeation chromatography method are as follows.

- As a GPC measuring apparatus, Tosoh Corporation HLC-8320GPC EcoSEC was used. The column temperature was set to 40.0°C, and the pump flow rate was set to 0.350 mL/min.

・Peak position (holding time)

Polymer P: Peak detected before 20 minutes (peak with shorter retention time and higher molecular weight than A-TMM-3LM-N and 4-HBA)

A-TMM-3LM-N: Sum of peaks 20.0-20.6 min and 20.6-21.5 min.

4-HBA: 21.7-22.4 minutes

- Measurement conditions: analyzed with a differential refractive index detector (RI detector).

(Preparation Example 3)

A resin mixture containing polymer P3 in which the MA unit of the raw material polymer 1 was ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water was prepared. Hereinafter, the detail is demonstrated.

First, 99.71 g of MEK was added to 60.00 g of raw material polymer 1 (0.312 mol in terms of MA) to prepare a solution. Next, 38.75 g of A-TMM-3LM-N was added to this solution, and 18.00 g (0.178 mol) of triethylamine was added after that, and it was made to react at the temperature of 70 degreeC for 2 hours. Furthermore, 56.27 g (0.390 mol) of 4-HBA was added after that, and it was made to react at the temperature of 70 degreeC for 4 hours, and the reaction solution was produced.

Subsequently, without post-treatment of the obtained reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, and the reaction solution was reacted at 70°C for 2 hours.

The aqueous phase was removed from the reaction solution by diluting the obtained reaction solution with MEK and treating with an aqueous formic acid solution and an aqueous citric acid solution. Furthermore, liquid-liquid extraction and then solvent substitution were performed in the same procedure as in Preparation Example 2, and the resin composition 3 was obtained. About the obtained resin composition 3, GPC measurement was performed, the amount of polymer P3, free polyfunctional (meth)acrylic compound, and free monofunctional (meth)acrylic compound contained in the composition, and the weight average molecular weight and polydispersion of polymer P3 degree was measured. A result is shown in Table 1.

(Preparation Example 4)

A resin mixture containing the polymer P4 in which the MA unit of the raw material polymer 1 was ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water was prepared. Hereinafter, the detail is demonstrated.

First, 100.30 g of MEK was added to 60.00 g of raw material polymer 1 (0.312 mol in terms of MA) to prepare a solution. Next, 58.12 g of A-TMM-3LM-N was added to this solution, and 18.00 g (0.178 mol) of triethylamine was added after that, and it was made to react at the temperature of 70 degreeC for 2 hours. Furthermore, 56.27 g (0.390 mol) of 4-HBA was added after that, and it was made to react at the temperature of 70 degreeC for 4 hours, and the reaction solution was produced.

Subsequently, without post-treatment of the obtained reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, and the reaction solution was reacted at 70°C for 2 hours.

The aqueous phase was removed from the reaction solution by diluting the obtained reaction solution with MEK and treating with an aqueous formic acid solution and an aqueous citric acid solution. Furthermore, liquid-liquid extraction and then solvent substitution were performed in the same procedure as in Preparation Example 2, and the resin composition 4 was obtained. About the obtained resin composition 4, GPC measurement was performed, the amount of polymer P4, a free polyfunctional (meth)acrylic compound, and a free monofunctional (meth)acrylic compound contained in the composition, and the weight average molecular weight and polydispersion of polymer P4 degree was measured. A result is shown in Table 1.

(Preparation Example 5)

A resin mixture containing the polymer P5 in which the MA unit of the raw material polymer 2 was ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water was prepared. Hereinafter, the detail is demonstrated.

First, 99.71 g of MEK was added to 60.00 g of raw material polymer 2 (0.312 mol in terms of MA) to prepare a solution. Next, 38.75 g of A-TMM-3LM-N was added to this solution, and 18.00 g (0.178 mol) of triethylamine was added after that, and it was made to react at the temperature of 70 degreeC for 2 hours. Furthermore, 56.27 g (0.390 mol) of 4-HBA was added after that, and it was made to react at the temperature of 70 degreeC for 4 hours, and the reaction solution was produced.

Subsequently, without post-treatment of the obtained reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, and the reaction solution was reacted at 70°C for 2 hours.

The aqueous phase was removed from the reaction solution by diluting the obtained reaction solution with MEK and treating with an aqueous formic acid solution and an aqueous citric acid solution. Furthermore, liquid-liquid extraction and solvent substitution were performed in the same procedure as in Preparation Example 2, and the resin composition 5 was obtained. About the obtained resin composition 5, GPC measurement was performed, the amount of polymer P5, a free polyfunctional (meth)acrylic compound, and a free monofunctional (meth)acrylic compound contained in the composition, and the weight average molecular weight and polydispersion of polymer P5 degree was measured. A result is shown in Table 1.

(Preparation Example 6)

A resin mixture containing polymer P6 in which the MA unit of the raw material polymer 2 was ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water was prepared. Hereinafter, the detail is demonstrated.

First, 100.30 g of MEK was added to 60.00 g of raw material polymer 2 (0.312 mol in terms of MA) to prepare a solution. Next, 58.12 g of A-TMM-3LM-N was added to this solution, and 18.00 g (0.178 mol) of triethylamine was added after that, and it was made to react at the temperature of 70 degreeC for 2 hours. Furthermore, 56.27 g (0.390 mol) of 4-HBA was added after that, and it was made to react at the temperature of 70 degreeC for 4 hours, and the reaction solution was produced.

Subsequently, without post-treatment of the obtained reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, and the reaction solution was reacted at 70°C for 2 hours.

The aqueous phase was removed from the reaction solution by diluting the obtained reaction solution with MEK and treating with an aqueous formic acid solution and an aqueous citric acid solution. Furthermore, liquid-liquid extraction and then solvent substitution were performed in the same procedure as in Preparation Example 2, and the resin composition 6 was obtained. About the obtained resin composition 6, GPC measurement was performed, the amount of polymer P6, a free polyfunctional (meth)acrylic compound, and a free monofunctional (meth)acrylic compound contained in the composition, and the weight average molecular weight and polydispersion of polymer P6 degree was measured. A result is shown in Table 1.

(Preparation Example 7)

A resin mixture containing a polymer P7 in which the MA unit of the raw material polymer 2 was ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water was prepared. Hereinafter, the detail is demonstrated.

First, 102.43 g of MEK was added to 60.00 g of raw material polymer 2 (0.312 mol in terms of MA) to prepare a solution. Next, 116.24 g of A-TMM-3LM-N was added to this solution, and 18.00 g (0.178 mol) of triethylamine was added thereafter, and it was made to react at the temperature of 70 degreeC for 2 hours. Furthermore, 56.27 g (0.390 mol) of 4-HBA was added after that, and it was made to react at the temperature of 70 degreeC for 4 hours, and the reaction solution was produced.

Subsequently, without post-treatment of the obtained reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, and the reaction solution was reacted at 70°C for 2 hours.

The aqueous phase was removed from the reaction solution by diluting the obtained reaction solution with MEK and treating with an aqueous formic acid solution and an aqueous citric acid solution. Furthermore, liquid-liquid extraction and then solvent substitution were performed in the same procedure as in Preparation Example 2, and the resin composition 7 was obtained. About the obtained resin composition 7, GPC measurement was performed, the amount of polymer P7, a free polyfunctional (meth)acrylic compound, and a free monofunctional (meth)acrylic compound contained in the composition, and the weight average molecular weight and polydispersion of polymer P7 degree was measured. A result is shown in Table 1.

(Preparation Example 8)

A resin mixture containing the polymer P8 in which the MA unit of the raw material polymer 1 was ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water was prepared. Hereinafter, the detail is demonstrated.

First, 97.74 g of MEK was added to 60.00 g of raw material polymer 1 (0.312 mol in terms of MA) to prepare a solution. Next, 58.12 g of A-TMM-3LM-N was added to this solution, and 18.00 g (0.178 mol) of triethylamine was added after that, and it was made to react at the temperature of 70 degreeC for 2 hours. Furthermore, after that, 27.00 g (0.187 mol) of 4-HBA was added, it was made to react at the temperature of 70 degreeC for 4 hours, and the reaction solution was produced.

Subsequently, without post-treatment of the obtained reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, and the reaction solution was reacted at 70°C for 2 hours.

The aqueous phase was removed from the reaction solution by diluting the obtained reaction solution with MEK and treating with an aqueous formic acid solution and an aqueous citric acid solution. Furthermore, liquid-liquid extraction and then solvent substitution were performed in the same procedure as in Preparation Example 2, and the resin composition 8 was obtained. About the obtained resin composition 8, GPC measurement was performed, the amount of polymer P8, free polyfunctional (meth)acrylic compound, and free monofunctional (meth)acrylic compound contained in the composition, and the weight average molecular weight and polydispersion of polymer P8 degree was measured. A result is shown in Table 1.

(Preparation Example 9)

A resin mixture containing polymer P9 in which the MA unit of the raw material polymer 2 was ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water was prepared. Hereinafter, the detail is demonstrated.

First, 99.86 g of MEK was added to 60.00 g of raw material polymer 2 (0.312 mol in terms of MA) to prepare a solution. Next, 58.12 g of A-TMM-3LM-N was added to this solution, and 18.00 g (0.178 mol) of triethylamine was added after that, and it was made to react at the temperature of 70 degreeC for 2 hours. Furthermore, after that, 40.51 g (0.281 mol) of 4-HBA was added, it was made to react at the temperature of 70 degreeC for 4 hours, and the reaction solution was produced.

Subsequently, without post-treatment of the obtained reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, and the reaction solution was reacted at 70°C for 2 hours.

The aqueous phase was removed from the reaction solution by diluting the obtained reaction solution with MEK and treating with an aqueous formic acid solution and an aqueous citric acid solution. Furthermore, liquid-liquid extraction and then solvent substitution were performed in the same procedure as in Preparation Example 2, and the resin composition 9 was obtained. About the obtained resin composition 9, GPC measurement was performed, the amount of polymer P9, a free polyfunctional (meth)acrylic compound, and a free monofunctional (meth)acrylic compound contained in the composition, and the weight average molecular weight and polydispersion of polymer P9 degree was measured. A result is shown in Table 1.

(Preparation Example 10)

A resin mixture containing polymer P10 in which the MA unit of the raw material polymer 2 was ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water was prepared. Hereinafter, the detail is demonstrated.

First, 100.03 g of MEK was added to 60.00 g of raw material polymer 2 (0.312 mol in terms of MA) to prepare a solution. Next, 58.12 g of A-TMM-3LM-N was added to this solution, and 18.00 g (0.178 mol) of triethylamine was added after that, and it was made to react at the temperature of 70 degreeC for 2 hours. Furthermore, after that, 27.00 g (0.187 mol) of 4-HBA was added, it was made to react at the temperature of 70 degreeC for 4 hours, and the reaction solution was produced.

Subsequently, without post-treatment of the obtained reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, and the reaction solution was reacted at 70°C for 2 hours.

The aqueous phase was removed from the reaction solution by diluting the obtained reaction solution with MEK and treating with an aqueous formic acid solution and an aqueous citric acid solution. Furthermore, liquid-liquid extraction and then solvent substitution were performed in the same procedure as in Preparation Example 2, and the resin composition 10 was obtained. About the obtained resin composition 10, GPC measurement was performed, the amount of polymer P10, free polyfunctional (meth)acrylic compound, and free monofunctional (meth)acrylic compound contained in the composition, and the weight average molecular weight and polydispersion of polymer P10. degree was measured. A result is shown in Table 1.

(Preparation Example 11)

Polymer P11 was prepared in which the MA unit of the raw material polymer 2 was ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water. Hereinafter, the detail is demonstrated.

First, 99.93 g of MEK was added to 60.00 g of raw material polymer 2 (0.312 mol in terms of MA) to prepare a solution. Next, 77.49 g of A-TMM-3LM-N was added to this solution, and then, 18.00 g (0.178 mol) of triethylamine was added, and the reaction was carried out at a temperature of 70°C for 2 hours. Furthermore, 56.27 g (0.390 mol) of 4-HBA was added after that, and it was made to react at the temperature of 70 degreeC for 4 hours, and the reaction solution was produced.

Subsequently, without post-treatment of the obtained reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, and the reaction solution was reacted at 70°C for 2 hours.

The aqueous phase was removed from the reaction solution by diluting the obtained reaction solution with MEK and treating with an aqueous formic acid solution and an aqueous citric acid solution. Furthermore, liquid-liquid extraction and then solvent substitution were performed in the same procedure as in Preparation Example 2, and the resin composition 11 was obtained. Then, the resin composition 11 was refine|purified by the following procedure.

· The polymer was reprecipitated with an excess of toluene.

- The operation of washing the polymer powder obtained by reprecipitation with an excess amount of toluene was repeated twice.

- Operation of washing the polymer powder after washing|cleaning the said 2 times with excess water was performed 3 times.

- The obtained reaction product was dried at 40 degreeC for 12 hours.

By the above, 34.35g of polymer P11 which ring-opened the structural unit derived from maleic anhydride in the raw material polymer 2 with A-TMM-3LM-N, 4-HBA and water was obtained.

(Preparation Example 12)

A resin mixture containing the polymer P12 in which the MA unit of the raw material polymer 2 was ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water was prepared. Hereinafter, the detail is demonstrated.

First, 99.93 g of MEK was added to 60.00 g of raw material polymer 2 (0.312 mol in terms of MA) to prepare a solution. Next, 77.49 g of A-TMM-3LM-N was added to this solution, and then, 18.00 g (0.178 mol) of triethylamine was added, and the reaction was carried out at a temperature of 70°C for 2 hours. Furthermore, 56.27 g (0.390 mol) of 4-HBA was added after that, and it was made to react at the temperature of 70 degreeC for 4 hours, and the reaction solution was produced.

Subsequently, without post-treatment of the obtained reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, and the reaction solution was reacted at 70°C for 2 hours.

The aqueous phase was removed from the reaction solution by diluting the obtained reaction solution with MEK and treating with an aqueous formic acid solution and an aqueous citric acid solution. Furthermore, liquid-liquid extraction and then solvent substitution were performed in the same procedure as in Preparation Example 2, and the resin composition 12 was obtained. With respect to the obtained resin composition 12, GPC measurement was performed, the amount of polymer P12, free polyfunctional (meth)acrylic compound, and free monofunctional (meth)acrylic compound contained in the composition, and the weight average molecular weight and polydispersion of polymer P12 degree was measured. A result is shown in Table 1.

(Preparation Example 13)

"Additive" of Table 1 was added to the resin composition 3 obtained by the method similar to Preparation Example 3 in the quantity shown by "additive amount" of Table 1, and the resin composition 13 was prepared. Here, the additive amount was taken as a weight ratio with respect to the solid content of the resin composition 3 (the total amount of the polymer P3 and the polyfunctional (meth)acrylic compound).

About the obtained resin composition 13, GPC measurement was performed, the amount of polymer P3, a free polyfunctional (meth)acrylic compound, and a free monofunctional (meth)acrylic compound contained in the composition, and the weight average molecular weight and polydispersion of polymer P3 degree was measured. A result is shown in Table 1.

In addition, the measurement conditions of the gel permeation chromatography method are as follows.

- As a GPC measuring apparatus, Tosoh Corporation HLC-8320GPC EcoSEC was used. The column temperature was set to 40.0°C, and the pump flow rate was set to 0.350 mL/min.

・Peak position (holding time)

Polymer P: peak detected before 19.3 min (peak with a shorter retention time and higher molecular weight than A-TMM-3LM-N and A-9550 and 4-HBA)

Polyfunctional (meth)acrylic compound (A-TMM-3LM-N and A-9550): Sum of 2 peaks in 19.3 to 19.8 minutes and 19.8 to 21.0 minutes

4-HBA: 21.7-22.4 minutes

- Measurement conditions: analyzed with a differential refractive index detector (RI detector).

(Preparation Example 14)

To the resin composition 12 obtained in the same manner as in Preparation Example 12, the "additive" of Table 1 was added in the amount shown in the "additive amount" of Table 1, and the resin composition 14 was prepared. Here, the additive amount was taken as a weight ratio with respect to the solid content of the resin composition 12 (the total amount of the polymer P12 and the polyfunctional (meth)acrylic compound).

About the obtained resin composition 14, GPC measurement was performed, the amount of polymer P12, free polyfunctional (meth)acrylic compound, and free monofunctional (meth)acrylic compound contained in the composition, and the weight average molecular weight and polydispersion of polymer P12 degree was measured. A result is shown in Table 1.

In addition, the measurement conditions of the gel permeation chromatography method are as follows.

- As a GPC measuring apparatus, Tosoh Corporation HLC-8320GPC EcoSEC was used. The column temperature was set to 40.0°C, and the pump flow rate was set to 0.350 mL/min.

・Peak position (holding time)

Polymer P: peak detected before 19.5 minutes (peak with higher molecular weight and shorter retention time than viscot #802 and A-TMM-3LM-N and 4-HBA)

Polyfunctional (meth)acrylic compound (A-TMM-3LM-N and biscoat #802): Sum of 2 peaks at 19.5 to 20.6 min and 20.6 to 21.5 min

4-HBA: 21.7-22.4 minutes

- Measurement conditions: analyzed with a differential refractive index detector (RI detector).

(Preparation Example 15)

Polymer P13 in which the MA unit of the raw material polymer 1 was ring-opened with a monofunctional (meth)acrylic compound was produced. Hereinafter, the detail is demonstrated.

First, 18.44 g of MEK was added to 10.00 g of raw material polymer 1 (0.052 mol in terms of MA) to prepare a solution. Next, to this solution, 9.38 g (0.065 mol) of 4-HBA was added, and thereafter, 3.00 g (0.030 mol) of triethylamine was added, and it was reacted at a temperature of 70°C for 6 hours to prepare a reaction solution.

The aqueous phase was removed from the reaction solution by diluting the obtained reaction solution with MEK and treating it with an aqueous citric acid solution. Thereafter, the polymer was purified by the following procedure.

· The polymer was reprecipitated with excess water.

- The operation of washing the polymer powder obtained by reprecipitation with excess water was repeated twice. The obtained reaction product was dried at 40 degreeC for 12 hours.

By the above, 9.5 g of polymer P13 which ring-opened the structural unit derived from maleic anhydride in the raw material polymer with 4-HBA was obtained.

About the obtained polymer P13, GPC measurement was performed, and the weight average molecular weight and polydispersity of the polymer P13 were measured. A result is shown in Table 1.

Moreover, disappearance of the peak of the monofunctional (meth)acryl compound used was confirmed by GPC measurement of polymer P13. Thereby, it confirmed that the unreacted monofunctional (meth)acryl compound was not contained in the obtained polymer P13.

(Preparation Example 16)

Polymer P14 in which the MA unit of the raw material polymer 2 was ring-opened with a monofunctional (meth)acrylic compound was produced. Hereinafter, the detail is demonstrated.

First, 18.44 g of MEK was added to 10.00 g of raw material polymer 2 (0.052 mol in terms of MA) to prepare a solution. Next, to this solution, 9.38 g (0.065 mol) of 4-HBA was added, and thereafter, 3.00 g (0.030 mol) of triethylamine was added, and it was reacted at a temperature of 70°C for 6 hours to prepare a reaction solution.

The aqueous phase was removed from the reaction solution by diluting the obtained reaction solution with MEK and treating it with an aqueous citric acid solution. Thereafter, the polymer was purified by the following procedure.

· The polymer was reprecipitated with excess water.

- The operation of washing the polymer powder obtained by reprecipitation with excess water was repeated twice. The obtained reaction product was dried at 40 degreeC for 12 hours.

By the above, 8.7 g of polymer P14 which ring-opened the structural unit derived from maleic anhydride in the raw material polymer with 4-HBA was obtained.

About the obtained polymer P14, GPC measurement was performed, and the weight average molecular weight and polydispersity of the polymer P14 were measured. A result is shown in Table 1.

Moreover, disappearance of the peak of the monofunctional (meth)acryl compound used was confirmed by GPC measurement of polymer P14. Thereby, it confirmed that the obtained polymer P14 did not contain an unreacted monofunctional (meth)acrylic compound.

(Preparation Example 17)

A resin composition 17 containing the polymer P15 in which the MA unit of the raw material polymer 2 was ring-opened with a monofunctional (meth)acrylic compound was prepared. Hereinafter, the detail is demonstrated.

First, 18.44 g of MEK was added to 10.00 g of raw material polymer 2 (0.052 mol in terms of MA) to prepare a solution. Next, to this solution, 9.38 g (0.065 mol) of 4-HBA was added, and after that, 3.00 g (0.030 mol) of triethylamine was added, and it was made to react at the temperature of 70 degreeC for 6 hours, and the reaction solution was produced.

The aqueous phase was removed from the reaction solution by diluting the obtained reaction solution with MEK and treating with an aqueous formic acid solution and an aqueous citric acid solution. Furthermore, liquid-liquid extraction and then solvent substitution were performed in the same procedure as in Preparation Example 2, and the resin composition 17 was obtained. About the obtained resin composition 17, GPC measurement was performed and the weight average molecular weight and polydispersity of the polymer P15 contained in the composition, the quantity of a free monofunctional (meth)acrylic compound, and polymer P15 were measured. A result is shown in Table 1.

In Table 1 below, the component used by each synthesis example and its input amount (maleic anhydride (MA) conversion) are also shown collectively.

[Table 1]

(Examples 1 to 12, Comparative Examples 1 to 5)

In each Example and each comparative example, the alkali solubility of the polymer P or resin composition obtained by the said preparation example was evaluated. Moreover, the photosensitive resin composition was prepared using these polymer P or resin composition, and the performance was evaluated.

<Evaluation>

[Evaluation of developability] (dissolution rate of polymer P in alkali developer)

Polymer P1 obtained in Preparation Example 1, Polymer P11 obtained in Preparation Example 11, Polymer P13 obtained in Preparation Example 15, and Polymer P14 obtained in Preparation Example 16 were dissolved in propylene glycol monomethyl ether acetate (PGMEA), and the solid content A solution having a concentration of 30% by mass was prepared.

Next, the above solutions or the resin compositions 2 to 10, 12 to 14, and 17 obtained in Preparation Examples 2 to 10, 12 to 14, and 17 are spin-coated on the wafer, the PGMEA is dried, and free for 2 minutes at a temperature of 100° C. By baking, a resin film with a film thickness of 2 µm ± 0.2 was produced.

This resin film was immersed in 2% sodium carbonate aqueous solution at a temperature of 23 degreeC for every wafer, and the dissolution rate of the resin film was measured.

The dissolution rate was calculated by visually observing the immersed wafer, measuring the time until the resin film was dissolved and the interference pattern was no longer seen, and dividing the film thickness by the time. A result is shown in Table 2. If the alkali dissolution rate is 180 nm/s or more, it can be used without any problem as a photosensitive material, if it is 300 nm/s or more, developability is favorable, and if it is 500 nm/s or more, it can be considered that developability is especially favorable.

[Sensitivity evaluation 1 of the photosensitive resin composition (exposure amount at which the residual film rate becomes 95% or more)]

First, the photosensitive resin composition which melt|dissolved the following components in propylene glycol monomethyl ether acetate (PGMEA) was obtained so that total solid content concentration might be set to 30 mass %.

-Polymer P1 (Polymer P1 of Preparation Example 1), Polymer P11 (Polymer P11 of Preparation Example 11), Polymer P13 (Polymer P13 of Preparation Example 15) or Polymer P14 (Polymer P14 of Preparation Example 16), or resin composition 2~ 10, 12-14, 17: 100 parts by mass

(Here, about the resin compositions 2-10, 12-14, 17, it weighed so that solid content (polymer P2-P10, P12, P15, and the total amount of a polyfunctional (meth)acrylic compound) might become 100 mass parts.)

-Polyfunctional acrylate (dipentaerythritol hexaacrylate): 50 parts by mass

・Photoinitiator (manufactured by BASF, Irgacure OXE01): 5 parts by mass

・Adhesive aid (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403): 1 part by mass

・Surfactant (manufactured by DIC Corporation, F-556): 0.5 parts by mass

The obtained photosensitive resin composition was spin-coated on a 3-inch silicon wafer treated with HMDS (Hexamethyldisilazane), and baked on a hot plate at 100°C for 120 seconds to obtain a thin film A having a thickness of 3.0 µm (±0.3 µm).

On this thin film A, through a photomask having a gradation of 1 to 100% light blocking, g+h+i line at an exposure amount of 100 mJ/cm ² with a g+h+i line mask aligner (PLA-501F) manufactured by Canon Co., Ltd. was exposed to

After exposure, the thin film was developed (immersed for each wafer) at 23° C. for 60 seconds in a 2.0 mass % sodium carbonate aqueous solution, to obtain a thin film B exposed and developed at each exposure dose of 1 to 100 mJ/cm ² .

From the film thicknesses of the thin film A and the thin film B obtained by the said method, the remaining-film rate was computed from the following formula|equation.

Remaining film ratio (%) = (thickness of thin film B/thickness of thin film A at each exposure dose) x 100

And the exposure amount used as 95 % or more of the remaining-film rate was made into the sensitivity of each photosensitive resin composition. A result is shown in Table 2. If the exposure amount at which the residual film rate becomes 95% or more is 60 mJ/cm ² or less, it can be used without any problem as a photosensitive material.

[Sensitivity evaluation 2 of resin composition (remaining film rate after exposure at low exposure dose)]

(Remaining film rate at an exposure dose of 5 mJ/cm ² )

The photosensitive resin composition prepared in the sensitivity evaluation 1 described above was spin coated on a 3-inch silicon wafer treated with HMDS (Hexamethyldisilazane), and baked on a hot plate at 100° C. for 120 seconds, 3.0 μm thick (±0.3 μm) thin film A got

On this thin film A, through a photomask having a gradation of 1 to 100% light blocking, g+h+i line at an exposure amount of 5 mJ/cm ² with a g+h+i line mask aligner (PLA-501F) manufactured by Canon Co., Ltd. was exposed

After exposure, the thin film was developed with 2.0 mass % sodium carbonate aqueous solution at 23 degreeC for 60 second (immersion for every wafer), and the thin film B was obtained.

From the film thicknesses of the thin film A and the thin film B obtained by the said method, the remaining-film rate was computed from the following formula|equation.

Remaining film ratio (%) = (thickness of thin film B/thickness of thin film A at each exposure dose) x 100

(Remaining film rate at an exposure dose of 10 mJ/cm ² )

The photosensitive resin composition prepared in the sensitivity evaluation 1 described above was spin coated on a 3-inch silicon wafer treated with HMDS (Hexamethyldisilazane), and baked on a hot plate at 100° C. for 120 seconds, 3.0 μm thick (±0.3 μm) thin film A got

On this thin film A, through a photomask having a gradation of 1 to 100% of light blocking, g+h+i lines at an exposure amount of 10 mJ/cm ² with a g+h+i line mask aligner (PLA-501F) manufactured by Canon Inc. was exposed

After exposure, the thin film was developed with 2.0 mass % sodium carbonate aqueous solution at 23 degreeC for 60 second (immersion for every wafer), and the thin film B was obtained.

From the film thicknesses of the thin film A and the thin film B obtained by the said method, the remaining-film rate was computed from the following formula|equation.

Remaining film ratio (%) = (thickness of thin film B/thickness of thin film A at each exposure dose) x 100

A result is shown in Table 2.

Sensitivity can be considered favorable as a residual-film rate is 50 % or more, and a sensitivity can be considered especially favorable as a residual-film rate is 80 % or more.

[Yellow Index]

The photosensitive resin composition prepared in the sensitivity evaluation 1 described above is spin coated on Eagle XG glass (made by Corning, 0.5 mm thick), and baked on a hot plate at 100° C. for 120 seconds, about 3.0 μm thick (± 0.1 μm) A thin film was obtained.

To this thin film, g+h+i line was exposed with an exposure dose of 100 mJ/cm ² with a g+h+i line mask aligner (PLA-600F) manufactured by Canon Corporation.

After exposure, the thin film was developed (immersed for each wafer) at 23° C. for 60 seconds in a 2.0 mass % sodium carbonate aqueous solution to obtain a thin film exposed and developed at an exposure dose of 100 mJ/cm ² .

The thin film was heat-treated at 230°C for 30 minutes under air. After the thin film was cooled under room temperature air, the thin film was again heated at 230°C for 30 minutes under air. The same operation was repeated, and heat treatment was performed three times in total for 30 minutes under air.

The yellow index (YI) of the thin film obtained by the above method was measured three times at different measurement locations using a colorimeter CR-5 (manufactured by Konica Minolta), and the average value was taken as the value of YI. The measurement type was transmission measurement, and the uncoated Eagle XG glass (made by Corning, 0.5 mm thick) was used for 100% calibration. A result is shown in Table 2. It can be said that heat discoloration resistance is favorable, so that the value of a yellow index is small, and if it is 1.35 or less, it can be used as a photosensitive material without a problem.

The results of developability evaluation and sensitivity evaluation are put together and shown below.

[Table 2]

The photosensitive resin composition of an Example had favorable alkali dissolution rate, therefore, was excellent in developability. The photosensitive resin composition of an Example has a high residual film rate at the time of exposure with an exposure amount of 10 mJ/cm< ² >, in other words, it hardens|cures with a low exposure amount, and it can be said that a sensitivity is high. Therefore, the photosensitive resin composition of an Example was equipped with the high sensitivity and the low yellow index with favorable balance.

<Production of color filter>

About the photosensitive resin composition prepared in Examples 1-12, the coloring photosensitive resin composition which added pigment dispersion liquid NX-061 (The Dainichi Seika Kogyo Co., Ltd. make, green) was further prepared in an appropriate amount.

This was formed into a film on a board|substrate, and the green color filter was able to be formed by performing exposure, alkali development, etc.

Moreover, as a pigment dispersion liquid, instead of NX-061, the blue or red color filter was able to be formed using NX-053 (blue), NX-032 (red), etc. manufactured by the company.

<Production of the Black Matrix>

With respect to the photosensitive resin composition prepared in Examples 1-12, the black photosensitive resin composition which added carbon black dispersion liquid NX-595 (made by Dainichi Seika Kogyo Co., Ltd.) in an appropriate amount further was prepared.

This was formed into a film on a board|substrate, and the black matrix was able to be formed by performing exposure, alkali development, etc.

This application claims priority on the basis of Japanese Application Japanese Patent Application No. 2019-189162 for which it applied on October 16, 2019 and Japanese Patent Application No. 2020-005974 for which it applied on January 17, 2020, and the disclosure All of is cited here.

Claims (21)

Polymer containing the structural unit represented by Formula (NB), and the structural unit represented by Formula (1); and
A resin composition comprising a compound having two or more (meth)acryloyl groups.
[Formula 1]

(In formula (NB), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a ₁ is 0, 1 or 2.)
[Formula 2]

(In formula (1), R ^p is group which has two or more (meth)acryloyl groups.) The method according to claim 1,
The resin composition in which the said polymer further contains the structural unit represented by Formula (2).
[Formula 3]

(In Formula (2), R ^s is group which has one (meth)acryloyl group.) The method according to claim 1 or 2,
The resin composition whose weight average molecular weights of the said polymer are 1000 or more and 20000 or less. 4. The method according to any one of claims 1 to 3,
The peak area derived from the compound having two or more (meth)acryloyl groups in the gel permeation chromatography (GPC) chart of the resin composition is 5% or more and 150% or less with respect to the peak area of the polymer. , the resin composition. 5. The method according to any one of claims 1 to 4,
The resin composition in which the said polymer further contains the structural unit represented by Formula (3).
[Formula 4]

6. The method according to any one of claims 1 to 5,
The resin composition in which the said polymer further contains the structural unit represented by Formula (MA).
[Formula 5]

7. The method according to any one of claims 1 to 6,
The resin composition which further contains the compound which has one (meth)acryloyl group. 8. The method of claim 7,
The peak area derived from the compound having one (meth)acryloyl group in the gel permeation chromatography (GPC) chart of the resin composition is 5% or more and 60% or less with respect to the peak area of the polymer, resin composition. 9. The method according to any one of claims 1 to 8,
The resin composition whose alkali dissolution rate is 250 nm/s or more. 10. The method according to any one of claims 1 to 9,
The resin composition further containing the organic solvent. 11. The method of claim 10,
The resin composition, wherein the solvent is at least one selected from propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, γ-butyrolactone, N-methylpyrrolidone and cyclohexanone. 12. The method according to any one of claims 1 to 11,
The resin composition used for formation of a color filter or a black matrix. Polymer containing the structural unit represented by Formula (NB), and the structural unit represented by Formula (1);
compounds having two or more (meth)acryloyl groups; and
A photosensitive resin composition comprising a photosensitive agent.
[Formula 6]

(In formula (NB), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a ₁ is 0, 1 or 2.)
[Formula 7]

(In formula (1), R ^p is group which has two or more (meth)acryloyl groups.) 14. The method of claim 13,
The photosensitive resin composition in which the said polymer further contains the structural unit represented by Formula (2).
[Formula 8]

(In Formula (2), R ^s is group which has one (meth)acryloyl group.) 15. The method of claim 13 or 14,
The photosensitive resin composition whose weight average molecular weights of the said polymer are 1000 or more and 20000 or less. 16. The method according to any one of claims 13 to 15,
The peak area derived from the compound having two or more (meth)acryloyl groups in the gel permeation chromatography (GPC) chart of the photosensitive resin composition is 5% or more and 150% of the peak area of the polymer. The following photosensitive resin compositions. 17. The method according to any one of claims 13 to 16,
The photosensitive resin composition in which the said polymer further contains the structural unit represented by Formula (3).
[Formula 9]

18. The method according to any one of claims 13 to 17,
The photosensitive resin composition in which the said polymer further contains the structural unit represented by Formula (MA).
[Formula 10]

19. The method according to any one of claims 13 to 18,
The photosensitive resin composition which further contains the compound which has one (meth)acryloyl group. 20. The method of claim 19,
The peak area derived from the compound having one (meth)acryloyl group in the gel permeation chromatography (GPC) chart of the photosensitive resin composition is 5% or more and 60% or less with respect to the peak area of the polymer. , a photosensitive resin composition. The hardened|cured material formed from the photosensitive resin composition of any one of Claims 13-20.

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